Production of higher boiling hydrocarbons from olefines



Patented Jan. 3,1939

UNITED STATES PRODUCTION OF HIGHER BOILING HYDRO- CARBONS OLEFINES vRichard M. Deanesly and Evan Clifford Williams, Berkeley, and Leo V. Steck, Piedmont, CaliL, assignors to Shell Development Company, San Francisco, Calif., a corporation of Delaware No Drawin Original application August 4,

8. 1934, Serial No. 738,536. Divided and this al plicatlon September 10, 1938, Serial No. 229,292

5 Claims. 01. zoo-ass) This invention relates to a process for the production of valuable higher boiling hydrocarbons from oiefines. It is also concerned with the production of valuable compositions of matter capa- 5 ble of use as fuels, as components of fuel mixtures,

as -lubricants,'as raw material for resin production, etc.

More specifically, this invention is concerned with the production of iso-octane and/or other htyglrocarbons boiling within the gasoline range or a ve.

Our invention may be practiced with mixtures of hydrocarbons containing olefines or with individual oleflnes. Assultable starting material we may employ hydrocarbons derived from mineral oils as petroleum;shale oil, and the like, or from natural gas or from coal, peat and like c'arboniferous natural materials. The olefines present in such starting material may be of natural occurreuse; the result of catalytic dehydrogenation, distillation, vapor or liquid phase cracking or other pyrogenetic treatment. Thus we may employ any suitable hydrocarbon mixture regardless v of its source or of its 'oleflne content.

We may proceed in several ways, depending on the product or products desired. For example, if individual or isomeric branched chain paramhs are desired, we may start with a suitable hydrocarbon fraction consisting essentially of, or predominating in, hydrocarbons containing the same numfines from their hydrocarbon fraction such as butane-butene, pentane-pentene, hexane-hexene, etc. cut, or by selectively absorbing a mixture of tertiary olefines without first fractionating, or partly fractionating the complex hydrocarbon mixture. Alternatively, we may absorb tertiary 5 and secondary-base olefines together from their fractions or mixtures but, in this procedure, control of the polymerization of the tertiary oleflnes is difiicult so that we prefer to absorb and polymerize the tertiaryand secondary-base oleilnes separately.

Secondary-base olefines are here defined as those olefines, both iso and normal, which yield secondary derivatives, while tertiary-base olefines are those iso-olefines which yield tertiary derivatives.

We have discovered that iso-octane and other valuable paraiiln compounds and mixtures may be simply and cheaply prepared by the selective and controlled polymerization of olefines and hydrogenation of the resulting polymers. Thus one distinguishing feature of our invention is the polymerization of oleflnes or oleflne mixtures of substantially the same reactivity; for example, tertiary-base olefines are polymerized without conversion of less reactive olefines, secondary-base, oleflnes are treated in accordance with their respective reactivities, ethylene is treated alone, etc. As a result, the polymerization of these olefines may be, for the first time, readily controlled to yield products of definite composition, for example, preponderantly dimers or trimers, etc., or mixtures of predictable proportions. By hydrogenation of these polymers, new compositions of matter are obtained, particularly suited for use as stable components or substitutes of fuels and lubricants.

For the purpose of aifording a clear under- I fines present in cracked petroleum oils which comprise a mixture of various unsaturated compounds, together with saturated hydrocarbon material. The latter may be considered as inert in our process. Straight run petroleum products are also useful, although usually containing lower oleflne percentages.

' The desired hydrocarbon fraction or mixture, in the gaseous, vaporous, or liquid state-the liquid state promoting increased surface contact-4s contacted with a polymerizing agent in any suitable manner; with or without pressure. For example, resort may be had to the agitation of the two agents in a common vessel or to countercurrent flow and the like. Suitable polymerizing agents are inorganic acids of which, H2804, HCl, H3PO4, HrP Oq and H3ASO4 are typical, or organic acids as its homoiogues, analogues, and the like or acid liquors such as are obtained by the absorption of olefines, of the same or less reactivity than the olefine or oiefines being treated, in mineral acting acids such as the above, or solutions or suspensions of acid acting salts as Ag:SO4, PbSOi. BiOCl, CUs(PO4)2 and the like. Preference is given polymerization agents of this type as they may also serve as media for the extraction, absorption or solution of the oleflnes. However,

i more reactive oleflnes have been removed. Such removal may be carried out by absorption in the above suggested media or by scrubbing with a chilled absorbent wash oil, for removal of amylenes and butylenes, for example, whereby the constituents recovered may be converted into val-" uable products in accordance with the present invention, or in other ways with other dispositions E of the products.

Following the removal of the tertiary base olefines by absorption in H2804, for example the secondary base olefines may then be absorbed in fresh acid in accordance with our invention for separate polymerization. I

The time of contact required for absorption and/or polymerization of the oleflne or oleilnes is dependent on the character of the oleilnes involved and the nature of concentration of the polymerizing agent used, as well as on the temperature at which the operation is carried out. For the production of substantially pure products, pure isomeric mixtures or mixed polymers ther'e=- of, it is necessary thatthe time of contact and temperature of the operation be so adjusted to the character and quantity of the more reactive oleflne or olefines present and the activity of the polymerizing agent used that negligible conversion of the less reactive oleflnes occurs.

It is to facilitate this selectivity of the procedure that we prefer to use a polymerizing agent Y such as H2304 and'the like above mentioned, in which the desired oleflne or oleilnes of approximately the same reactivity may be absorbed. The polymerization of the absorbed oleflnes may then be completed under the conditions best adapted to their polymerization rate to yield a preponderance of dimer, trimer, or other forms or mixtures as desired. a i V.

In such cases the absorption of the desired olefine oroleflnes is effected by adjustment of the strength of the acid used, to the previously men tioned controlling factors. Thus lower temperaatures and/or a higher rate of thruput may be used with stronger acids, whereas with relatively weak acids higher temperatures may be maintained with or without a decreased rate of oleiine thruput. The polymerization is then effected by subjecting the absorbed oleflne to more drastic. treatment as by further heating, etc. The polymerization of secondary base oleilnes is more diflicult than the polymerization of the tertiary base oleflnes and usually requires higher temperatures and/or more concentrated acid or the use of more reactive polymerizing agents. Increased reaction time'promotes the formation of higher polymers as does increased temperature. The latter, however, may tend to produce undesirable reactions with the acid present. Additional polymerizing agents may advantageously be added to promote the formation of higher polymers, as for example, by increasing the concentration of the acid being used or by the addition of other agents such as A101: and the like. In the latter case the operation is preferably carried out in steps, the product of the acid polymerization, most preferably rectified, being separately treated phate, and the like.

tions, room temperature for example, with the more active catalyst. r

The hydrogenation of the resulting desired polymer or polymeric mixture is effected by any conventional procedure, the conditions being so adJusted that substantial decomposition is not produced. Suitable active catalysts are metals of the 1st, 6th, and 8th groups of the periodic table, either alone or in combination with each other or other metals or with inert supports, for example, copper, tungsten, platinum black, copper chromite, copper and nickel with zinc or cobalt, nickel on pumice or alumina, etc; The oxides, sulfides and phosphates of these metals and particularly those of the 6th group may also be used, as chromic oxide gel, molybdenum phos- Any suitable source of hydrogen may be employed. In addition to the economic advantage of using dilute by-product hydrogen, such gases are particularly useful for temperature control of the hydrogenation reaction in the vapor phase.

The temperature and pressure necessary for the hydrogenation are dependent both upon the activity of the catalyst employed and the nature of the polymer. Thus with colloidal palladium, for example, active hydrogenation of diisobutylene can be effected at room temperature, whereas the more common types of'nickel catalyst requires temperature of over 100 C. and pressure of l0'atmospheres or more. Furthermore with triisobutylene even higher temperatures are required under comparable conditions to make the hydrogenation rate practical. The upper tem perature limit, as mentioned above, is fixed by the tendency of the particular polymer involved to decompose which in our process is to be avoided.

The following detailed example illustrates one modification of our invention as applied to the production of substantially pure iso-octane; But it will be understood that many widely diiferent embodiments of this invention may be made without departingfrom the spirit thereof, and that by suitable modification of operating conditions a great variety of -other compounds and mixtures may be prepared.

For the production of iso-octane (2,2,4 trimethyl pentane) a hydrocarbon fraction containing substantially only compounds of 4 carbon atoms to the molecule is preferred. The presence of compounds containing fewer carbon atoms to the molecule does not materially effect the procedure, however, but the presence of oleflnes of a greater number of carbon atoms to the molecule tends to give lower yields of iso-octane as a result of the formation of mixed polymers and requires more exacting fractionation of the resulting products.

The desired butane-butane fraction, having for example, a boiling range of about -l0 C. to about plus 5 0., obtained by distillation or condensation or both will normally contain: Normal and iso-butane, butene l and butene 2, isobutylene, and traces of dioleflnes such as butadiene.

In the practice of our invention for the production of substantially pure iso-octane from such starting material we preferably .employ H2804 of about to 75% strength as it apperently yields the best results. The rate of thruput of butane-butane mixture is about 0.6 gallon per minute per gallon of reaction space where the isobutylene content is about 18% by weight employing 0; H2804. Under these conditions about 0.5 gallon of acid are used per under carefully controlled temperature condigallon of butane-butene mixture. The temperature is preferably maintained in the above example at about 50 C. It is to be understood that the above conditions illustrate one combination of these factors only and that within wide limits changes made in any one of them may be com- :pensated for by changes in the others and the same approximate result attained. Furthermore, with fractions containing hydrocarbons of different reactivity modifications apparent to the chemist will be'necessary.

Under the above conditions the isobutylene is selectively absorbed by the H2804 and may be drawn off for completion of the polymerization thereof, leaving a butane-butene mixture which is eminently suitable for the preparation of secondary butyl alcohol. or by suitable modification of the methods of the present invention, for the production of isomeric octanes.

For completion of the-polymerization of the isobutylene the acid solution thereof is heated, either in a closed vessel with stirring, or while flowing through a coil, to about .80 to 110 C.

until polymerization is.practically complete. In

batch operation in an autoclave this will be indiprovides a simple means for carrying out this operation. Other means and other temperatures may be employed, but it has been found that lower temperatures require longer time of treatment and ultimately lead to great increases in the proportion of triisobutylene and indeed serve as a ready means for preparing this compound whereas for the production of iso-octane, the product desired is the dimer. A temperature as high as 140 C. also increases the yield of triisobutylene, butat the same time leads to the formation of SO: and malodorous compounds by the interaction of 802 and/or H2304 with the polymers, which we prefer to avoid.

The rate of thruput of the acid-isobutylene mixture depends upon the composition of the mixture and the rate of heat transfer provided. In continuous operation using a coil heater, when the capacity of the apparatus is exceeded, it is shown by increased amounts of unpolymerized isobutylene in the crude polymer or, in extreme cases, loss of gaseous isobutylene. 1

Good results have been obtained with a copper coil of cross-section such that it handles 50 to 80 gallons of isobutylene-acid mixture per hour per square inch internal cross-section and of a length sufficient to provide /2 square foot of surface per gallon of feed per hour. In this way polymer yields of 90% of the isobutylene input are obtainable. Under the above conditions the crude polymer contains from 60-to 70% diisobutylene by volume, the remainder being principally trimer. At some sacrifice of capacity, the diisobutylene content may be increased to 75 to 30% by the addition of water to'dilute the feed to the polymerizing coil. This dilution water is of the order of about 10% by weight of the acid input (1. e., on a hydrocarbon free basis.)

The capacity of a coil of a givensize can be increased by providing an unheated insulated waiting tank preferably in the form of a fairly short, broad tower into which the contents of the polymerizing coil discharge at the bottom and bubble up through acid which tends to settle back. The mixture'of polymer and acid is then conducted through cooling coils to a separator where the acid is withdrawn for recycling and the crude polymer collected in a storage tank over a layer of alkali to remove any traces of dissolved acid.-

Rectification of the crude polymer containing, under the conditions of preparation described, diisobutylene and triisobutylene in an approximate ratio of 3:1 is a simple operation. The

diisobutylene is recovered as the fraction boiling between 99 and 105 C.

' The hydrogenation of the diisobutylene may readily be carried out in a steel autoclave equipped with a stirrer and the necessary valves to permit maintenance of an atmosphere of hydrogen not only during the time of reaction, but also during charging and discharging. At the conclusion of each run the active nickel catalyst, present in an amount about equal to 5% by weight of the diisobutylene to be hydrogenated, is allowed to settle. The clear iso-octane is drawn off as completely as possible, preferably with the aid of a filter, and the autoclave recharged with fresh diisobutylene for the next run. The course of the reaction may be followed by withdrawing samples from the vapor phase (to prevent a removal of catalyst), condensing the hydrocarbons present, and determining their bromine number or refractive index. We have found that the hydrogenation of diisobutylene of sufficiently low sulfur content proceeds smoothly in the apparatus described at about 150 C. and

about 225 pounds per square inch pressure, and,

is complete in about 15 minutes. Pressmes above about 225 lbs./sq. in. produce very little change in the reaction rate, while those as low as 175 lbs./sq. in.- show distinctly low rates. In the region between 105 and 165 C. the rate of hydrogenation is increased by about per degree increase in temperature. The hydrogenation may be carried out inthe vapor phase as by passing diisobutylene vapor and hydrogen through a tube containing active nickel supported on pumice at a temperature of about 200 to 300 C. and under a pressure of about 150 to 250 lbs./sq. in. Difficulty has been encountered, however, in preventing the development of excessively high temperatures due to the heat produced by the reaction. Inert gases such as nitrogen and the like may be present in the hydrogenating system.

, The preferred nickel catalyst is prepared by slowly heating technical nickelous formate suspended in oil to 300 C. and holding the temperature at that point for three hours, an atmosphere of hydrogen being maintained at all times. The mixture is cooled and the nickel settled by centrifuging.

the sulfur content may alsobe reduced to safe limits. The excess sulfur may alternatively be eliminated from the polymer by suitable chemical treatment as by refluxing with H202 or other oxidizing agents, washing with Hg(N0s) 2 and the like, or by absorption using silica gel or active nickel, etc. None of these alternatives have been found as satisfactory or as economical as the preferred treatment of the starting material.

By following the preferred procedure outlined above substantially theoretical yields of iso-octane having the following characteristics may be obtained:

duced, and some remarks regarding their prepaabove-mentioned iso-octane and isododecane mixture with an iso-pentane fraction, recoverable by repeated distillation of petroleum oils, forms another high octane value fuel. The same product may also be obtained by inclusion of isopropyl ethylene in the mixed polymers before hydrogenation.

It is thus seen that our invention provides a commercially available method for producing a wide variety of valuable branched chain paraflin hydrocarbons containing tertiary carbon atoms either as substantially pure chemical individuals or isomeric mixtures. These products are pro-- ducible in high yield from cheap widely distribration. uted raw materials by a simple procedure which Hydrogenation product Hydrocarbon Selectively ahi on sorbed component Realm Dimer Trimer Mixture Gaseous fraction Ethylene N-butane 3 methyl pentane. Le st reactive of the oleiinee. Requires boiling below very drastic acid treatment and high -z0 temperature.

Propylene. imethylpentane. 2,4 dimethyl hep- Isohexane and May be selectively removed b treattane. isononane. ment with 80-l00% 11,80 at Si -30 C.

or by fractionation.

hutanebutena... Isobutylcne 2,2,4 trimethyl I s o d o d e c a n e Iso-octaneand 'lrimer most easily recovered as azeopentane. (chieiiy2, 2, 4, 4, ilo-dodectrope I}. P. 98 0. (approximately 51 to 6 pentamethyl sue. 63% triisobutylene and 40 to 47% water heptane). by volume). Hydrogenation of triisobutylene is much slower under comparable conditions than diisobutylene. Composition of mixture can be varied between iso-octane 30 to 90% and isododecane 70 to 10% by control of conditions of polymerization.

Butane l and bn- Mixture'a moth Mixed dodecanes.. Mixed iso- Reqnires use of stronger acid and higher tone 2. heptane and 3,4 mers oi isotcmperature with or without decreased dimethyl hexoctane and rate of throughput as compared with ans. isododecane. tertiary base oleflnes.

Pentane-pentene.. Tertiary base ole Mixture 3,3,6 trl- Mixed penta-dec- Mixedisomer- These materials are of only slightly lines (trimethyl methyl lieptane anes. ic decanes lower reactivity than isobutylene and ethylene and and 3,3,4,5 tetand pent when treated under the same condiunsymmetrical ramethyl hexdecanes. tlons give about the same results as methyl ethyl ane. regards degree of polymerization, etc. ethylene).

Isopropylethylene. 2,3,6 trimethyl Mixed isopenta- Isopro ylethylene preferably isolated by heptane. decancs. fractionation but may also be treated with minus 1 and pentene 2 by the descri procedure. 1.

Secondary base Mixture of 5 iso- Mixed pants-deo- Require slightly more drastic conditions olefin (pen- 'meric decanes. anee. than are y with butane 1 and tone 21) and penbutane 2. 1. tone much greater value and usefulness than the mixtures of graduated composition produced by former processes. For example, the iso-octane, isododecane mixture obtainable by hydrogenating the crude polymer obtained as an intermediate in the preparation of lac-octane as described, is a fuel boiling within the gasoline range, of much higher anti-knock rating than any paraiiln hydrocarbon mixture or similar makes these products available, for the first time, in a valuable form at prices which permit their commercial use.

Two particularly novel high octane fuels which are of high volatility and desirable for high speed internal combustion engines, particularly planes, are fuel containing:

15% isopentane 85% iso-octane Boiling range 31'. to 99 15% isopentane iso-octane isododecane While we have in the foregoing described in some detail the preferred embodiment of our inauaosv vention and some variants thereof, it will. be understood that this is only for the purpose of making the invention more clear and that the invention is not to be regarded as limited to the details of operations described, nor is it dependent upon the soundness or accuracy of the theories advanced as to the advantageous results attained.-

This application is a division of our copending agzfiication Serial No. 738,536, filed August 4, 1

We claim as our invention:

1. 'A process for preparing selected valuable higher boiling hydrocarbons from mixtures comprising oleflnes of difierent orders of reactivity including tertiary oiefines which comprises preliminarily removing substantially all of the tertiary olefine content thereof, polymerizing a major portion of the less reactive oieflne content and hydrogenating at least part of the resulting polymerization product.

A process for preparing selected higher boiling hydrocarbons which comprises preliminarily removing substantially all of the tertiary oleflne content from a hydrocarbon mixture comprising significant quantities of secondary and tertiary oleflnes, polymerizing amajor portion of the remaining secondary oleflne content and hydrogenating at least part of the resulting polymerization product.

3. A process for preparing selected higher boiling hydrocarbons from a hydrocarbon mixture comprising secondary and tertiary olefines in the liquid phase which comprises preliminarily removing substantially all of the tertiary olefine content thereof, polymerizing a substantial portion of the secondary oieflne content thereof and hydrogenating at least part of the resulting poly-. merization product.

4. A process of preparing selected higher boiling hydrocarbons from a hydrocarbon mixture containing ethylene, secondary and tertiary olefines which comprises substantially removing the secondary and tertiary oleflne content, polymerizing a substantial part of the residual olefinic content and hydrogenating at least part of the resulting polymerization product.

5. A process for preparing selected higher boiling hydrocarbons from a hydrocarbon fraction predominating in hydrocarbons of the same number of carbon atoms to the molecule and I containing secondary and tertiary olefines which comprises preliminarily removing substantially all of the tertiary olefine content thereof, polymerizing a major portion of the secondary oleflnic content thereof and hydrogenatingat least part of the resulting polymerization product.

RICHARD M. DEANESLY'. EVAN CLIFFORD WILLIAMS. p LEO V. STECK. 

